Sulfur dye and process of making same.



UNITED STATES Parana. OFFICE.

WILHELM HE RZBERG, OF BERLIN, OSWALD SCHARFENBERG, OF SCHONEBERG, AND MAX BONUS, OF BERLIN, GERMANY, ASSIGNORS TO AGTIEN GESE LLSOHAFT FUR ANILIN FABRIKATION,'OF BERLIN, GERMANY.

SULFUR DYE AND PROCESS OF MAKING SAME.

No. se4,o44.

I Specification of Letters Patent.

Patented Augf27,

Application filell June 3,1907. Serial No. 377,069.

' vented certain new and useful Improvements in New in which formula R means an ary'l-group such as for instance 0 11 or OH .G E,,, and \R, signifies another radical, such as for instance chlorin or'ahydroge n atom. The reaction may be performed in an aqueous sol'ution, more or less concentrated, as well as with the aid of another solvent, such as for instance alcohol.-

, We have furthermorefound, that the newsulfurized products thus formed still contain the residue of the respective arylsulfonic acid and that, when this residue is eliminated in a suitable manner, very valuable dyestuffs are obtained which dye cotton directly, from a bath containing an alkali-sulfid, clear and deep blue shades which show a very good iastness to'washing and light and are fast to acids; whereas the abovenamed intermediate compounds dye also cotton without a mordant blue'tints, but which tints are not fast to acids.

The reaction, which underlies our present inven-' tion, therefore proceeds in two steps; as to the second step, namelythe elimination of the residue of the 1 'respective arylsulfonic acid, it may-be effected in i any suitable manner, for instance bythe'action of concentrated sulfuric acid.

The following examples serve to illustrate our invention, the parts being lay-weight.

Example 1): Production of the intermediate compoundfrom the para-tolue'rwsulfonic derivative of para-aminopara orcydiphenylamr'nr Y OH.O H LNH.G,H .NH.SO,.G,H .GH,. (4)( )T 180 parts of this body are introduced into. asolution of sodiumpolysulfid, which is prepared by melting together 620 parts of crystallized sodiumsulfid parts ofsulfur and adding to the melt 275 parts-of water.

This mix i h n heated F9 ai sr'e i '10 parts of the intermediate compound are dissol.

ara -oxydiphenylaminl ized product is separated in the manner asusual for sulfurized dyestuffs. For-instance a current of air is introduced into'the reactionmass after diluting it with water, whereby the dyestuff is'precipitated and is isolated by filtering and drying. Thus isobtained a powder of a copper-like luster, which easily dissolves in water with a pure blue coloration, from which solution thenew product is separated in the shape of red-hrownfiakes by the addition of an acid, these redbrownflakes on their part again easily dissolve in boiling diluted soda-lye. I This new sulfurized body dyes cotton-blue tints, which are not fast to acids. I

' Example 2): Production of the dyestufi' from the intermediate compound by eliminating the residue:

so,.o,n,.on,.

while agitating well in 30 parts of concentrated sulfuric acid; the mass is then poured on ice and the dyestuff isolated by filtering, washing with water, which to the end of the washing operation is added with some sodium-carbonate in order to remove the restv of the sulfurio. acid-used, and drying. Thus is obtained a dark powder of a bronze luster, which is insoluble in waterand in a boiling diluted soda-lye as well as in the usual apparatus, during 48 hours, whereafter a yellow-brown solution is obtained, from which solutionthe sulfurorganic solvents. Byconcentrated sulfuric acid the dyestuff is dissolved with a reddish-blue coloration, from which solution by the addition of ice the product is again precipitated. -This new product dyes cotton without a mordant from a bath containing an alkali-sulfid, clear and deep blue shades which are fast to acids and are of a very good fastness to washing and to light. The fact that the tints obtained with this dyestuff are directly, 1. e. without a subsequent treatment with copper salts, fast to washing is very characteristic for the new dyestuff. i

Of course, as stated in the preamble of the specifica tion, instead of the para-'toluenesulfbnic derivative of para-amino-para'-0xydiphenylamin used in the foregoing example for instance'the corresponding benzenesulfonic derivative may be used. a

' Among other derivatives of the above-given general formula,.which are tobe treated with an alkali-polysulfid according to oil r present invention, we name for instance the para-toluene-sulfmpara-amidameta-chloroonqn unom,

(1 NH.so,.c,n,.oH,. 4 I 1 This arylsulfonic deriyative, when-converted into a sul' I urized dycstuff according to our present invention, yields on cotton, from a bath containing an alkalhsulfid,

clear and deep red-blue tints which are directly fast to washing and light, and to acids. This dyestufi is a dark powder oi'a brown. luster, which is insoluble in water and in boiling diluted sodalye'; also insoluble in the usual organic solvents. Inconcentrated sulfuric,

acid it dissolves to a violet colored solution, from which colored flakes. I

It is obvious to those skilled in the art that our pressolution the dyestuff is again precipitated in blue bIaCk ent invention is not limited to the foregoing examplesor to the details given therein. First it may be stated, that not only the proportion of the aikali-polysulfid in respect to the proportion of the parent material to be treated therewith, may-bev varied within wide limits 3 Without esse1itial'ly; 'changing the result, but also the proportions oi-theal alimonosulfid in respect to the proportions of the su ur, from which'proportions the character of the allialipolysulfid to be used depends as a .disulfid, or tri-,o.tetr-aor pentasul fid, etc., can be changed-to a great extent wi thout'departing from the y scope of our presentinvention Furthermore,-as to the medium or media, Within which the reaction'asaccording to' our present invention may be carried out; for the aqueous solution employed inthe foregoin'gexample other medium or-media may be employed, such as for instance an alcoholic-aqueous' solution or-an alcoholic solution or the like. :Of course the'special conditions of i the reactionmust then be selectedso'as to'suii; the nature ofthe medium employed as well as of the pm'entmaterial and of the reaction product in order to obtain ptheibest results. Finally it is convenient tosay that the elimination of the residue of the respective'arylsul fonic acid, for instance of the. group? SO C H CH may be efiected in any. suitable wayother than that given in the above example.

Now what we claim is:-,

1. The herelnhefore-described manufacture of new sulnew dyestuffs DyeIiminaiing the residue of "scribed new sulfurized dyestuffs, dyeing cotton without it mordant clear blue tints which are directly, namely 'ith out a subsequent treatment with copper salts, fast towash ing, which tints are also fast to'light and to jucids, which dye'stutfs may be obtained by acting with annlkaJi-polysuliid upon an urylsulfonic derivative of an amidooxy-compound of the general formula as defined in thev foregoing specification and converting the sulfurized intermediate compound into-"the dyestuffs by eliminating the residue of the respective arylsulf'onic acid these dyestuffs being in the dry state dark powders of a brorilie luster, which .are

insoluble in water and in boiling diluted soda-lye as well as in the usual organic solvents, and wh'ichdyestuffs dis-i solve in concentrated sulfuric'acid to from blue to violet.

colored solutions, frornvwhich solutions the dyestuffs are again ire'cipita'tedby the addition of ice.

As a new article'of manufacture the hereinbeforer described blue'sulfurized dyestuif, whiclrl'rnay be obtuined is acting with sodium-pentasulfid ubon para to1i1ene-snlfo-.

para-amidoqiara-oxydiphenylainin' in aqueous solution, 'andeliminating from the sulfurized intermediate compound the residue: SO .'C HJ,.CH' by the action. of concentrated sulfuric acid, which dyestuff dyes cotton without a mor dant a clear deep bluetint; which tint is directly, na'mely without i1 subsequent-treatment with acoppei' salt, fast to washing, and which tintis'also fast to light and to acids. this dyestufljf beingin the dry state a dark powder ofa bronze luster, which is insoluble-inwater and in a boiling diluted soda-lye as well as in .the usual organic solvents, and whichdyes tufi dissolves in concentrated sulfuric acid to a reddish blue colored solution, from which solution the dyestuifis' a-gain precipitated by the addition of ice.

In testimony whereof we have hereunto set our hand in prescnceof two subscribing witnesses. I

' wrLHELM I-IERZBERG'.

OSWALD SCIIARFENBERG; MAX BONUS. Witnesses WoLornmn HAUPT,

HENRY IIASPER. 

